Water-insoluble styryl dyestuffs

ABSTRACT

A water-insoluble styryl dyestuff of the formula   IN WHICH Y1 represents hydrogen, methyl or methoxy, Y2 hydrogen or methoxy, A lower alkylene which may contain a further group of the formula -OCOB, Z stands for a member selected from the group consisting of lower alkyl, phenyl-lower alkyl, lower alkanoyloxylower alkyl and the group of the formula -A-OCOB and B is a member selected from the group consisting of phenyl which may be substituted by chlorine, lower alkyl, lower alkoxy, lower carbalkoxy or hydroxy groups, thienyl, lower carbalkoxy-thieneyl, phenyl, styryl, phenoxymethyl and phenacetyl.

United States Patent 1 1 Ramanathan 1 1 Mar. 4, 1975 i 1 WATER-INSOLUBLE STYRYL DYESTUFFS [75] Inventor: Visvanathan Ramanathan, Basel.

Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Jan. 3, 1968 I21] Appl. No.: 695,346

Related U.S. Application Data [30] Foreign Application Priority Data Mar. 9. 1964 Switzerland 2993/64 Feb. 11. 1965 Switzerland 1886/65 [52] U.S. Cl 260/465 D, 260/2949, 260/3305, 260/3474 [51] Int. Cl C07c 121/60, C07C 121/70 [58] Field of Search 260/465 D, 465 E [56] References Cited UNITED STATES PATENTS 2.206.106 7/1940 Muller ct al. 260/465 D 2.226.054 12/1940 l clix ct a1 260/465 D 2, 83,551 l/l952 Dickey ct Zli 260/465 D 2. 83.551 1/1952 Dickey ct a1 260/465 2. .6l4 l/l952 Taylor ct al. 260/465 D 2.850.520 9/1958 Mcrian ct all. 260/465 D 2.936.319 5/1960 Mcrian et al. 260/465 D 3.106438 10/1963 Converse et al. 8/39 3.189.398 6/1965 Pizzarello et al. 8/39 OTHER PUBLICATIONS Yenkataraman. Chemistry of Synthetic Dyes. (Academic Press. New York. 1952) p. 1220. Vol. 11.

Morrison et al.. Organic Chemistry. (Allyn and Bacon. Boston. 1959) pp. 7l72.

Primary IirunzinerJoseph Paul Brust Attorney. Agent. or Firm-Joseph G. Kolodny; Edward McC. Roberts; Prabodh l. Almaula [57] ABSTRACT A water-insoluble styryl dyestuff of the formula in which Y represents hydrogen. methyl or methoxy. Y hydrogen or methoxy. A lower alkylene which may contain a further group of the formula OCOB. Z stands for a member selected from the group consisting of lower alkyl, phenyl-lower alkyl, lower alkanoyloxy-l'ower alkyl and the group of the formula AOCOB and B is a member selected from the group consisting of phenyl which may be substituted by chlorine. lower alkyl. lower alkoxy, lower carhalkoxy or hydroxy groups, thienyl, lower carbalkoxythieneyl. phenyl, styryl. phenoxy'methyl and phenacetyl.

12 Claims, No Drawings WATER-INSOLUBLE STYRYL DYESTUFFS This application is a continuation-in-part of application Ser. No. 436,666, filed Mar. 2, 1965, nowabandoned.

The present invention provides new water-insoluble styryl dyestuffs of the formula ,A OCO (CHp E IO IB,

in which in and p represent 1 or 2, and n l to 3, p being 1 only when .n is 3.

In the scope-of the present invention it is mainly dyestuffs of the formula that are of interest, in which formula Y, represents a methyl group or a methoxy group, Y represents a hydrogen atom or a methoxy group, B represents a benzene or thiophene radical which maybe substituted, A represents an alkylene group whichmay contain an acyl group, and Z represents a lower alkyl group, a phenalkyl (preferably benzyl) group or an acyloxyalkyl (lower alkyl) group, especially a radical of the formula in which m and p are l or 2 and n l to 3, 2 being 1 only when n is 3.

In this Specification the term lower alkyl groups refers to alkyl radicals containing 1 to 6 carbon atoms. Dyestuffs of the invention that are of special interest are those of the formula in which Y, represents a methyl group or a methoxy group. Y represents a hydrogen atom or a methoxy group, Z represents the radical AOCO-B', A represents an alkylene group with 2 to 3 carbon atoms that may contain the grouping -O-COB' as -O- acyl radical and B represents a benzene or thiophene radical that maybe substituted.

The most representative ofthe compounds ofthe'formula (lb) are styryl derivatives of the formula CH OH OC0-B (1 maQ-m No 0H cH oc0B' in which Bhas the meaning given above.

A particular variant of the invention includes, for example, water-insoluble styryl dyestuffs of the formula NC\ Z" (1d) cam-QR NC/ n (0co )2 in whichZ represents an alkyl radical containing 1 to 6 carbon atoms,.A" represents an alkylene radical containing l to 6carbon atoms and 15 represents a benzene or thiophene radical that may be substituted, and the dyestuffs of the formula Y N 2 CH 2 (1-8) c-c rr B.

.NG ll-000% p n-l m-l in which Y represents a methyl group or a methoxy group, Y represents a hydrogen atom or a methosy group, B" represents a benzene or thiophene radical that may be substituted and A represents an alkylenc group that may contain an Oacyl group, constitute another variant.

The new dyestuffs maybe obtained when a. an aldehyde free from groups imparting solubility in water and corresponding to the formula or an aldimine thereof is condensed with malodinitrile or a cyanoacetic acid alkyl ester, the symbols A, B, Y Y Z, In and n in the formula (2) having the meanings given above, or b. when 1 mol of a. styryl derivative of the formula N 2 z (3) main-Q11 l \AOH in which A, X and Y have the meanings given above and Z, represents an alkyl or a hydroxyalkyl group, especially a hydroxyethyl group, is acylated with l mol of a halide or an anhydride of a carboxylic acid of the formula especially a benzene carboxylic acid, and with 1 mol of a halide or an anhydride of an aliphatic or a cycloaliphatic monocarboxylic acid or of a carboxylic acid of the formula especially a benzene carboxylic acid. Molecule doubling can also be achieved when acylation is carried out with an appropriate dicarboxylic acid derivative instead of with a monocarboxylic acid derivative (as indicated above).

Starting materials specially suitable for method a of the process of the invention are aldehydes of the formula CH CH A0 0H0 N in which Ac represents the radical of a lower aliphatic monocarboxylic acid or a benzoyl radical and B2 represents a benzoyl radical. The benzoyl radicals may contain further substituents that do not impart solubility in water, for example, halogen atoms, alkyl, alkoxy or carbalkoxy groups. Among the aliphatic acyl radicals there may be mentioned, in particular, the radicals of acetic acid, propionic acid and butyric acid. The following aldehydes are examples:

CH CH Condensation of the aldehydes with malodinitrile or a cyanoacetic acid alkyl ester is advantageously carried out with the application of heat in the presence of a basic catalyst, for example, ammonia, dimethylamine, diethylamine, piperidine, piperidine acetate, sodium alcoholate or potassium alcoholate, if necessary, in the presence of a solvent, for example, methanol, ethanol. benzene, toluene, xylene, chloroform or carbon tetrachloride. When using solvents the water formed during the reaction can be removed from the reaction mixture continuously by azeotropic distillation of the said solvents, which process steadily shifts the reaction equilibrium in favour of t'he'condensation product. The condensation process may also be carried out in glacial acetic acid without the use of a basic catalyst or in some other organic acid, or in the absence of a solvent by fusing-the reactants in the presence of a basic catalyst, for example, ammonium acetate or piperidine acetate.

Instead of the aldehydes it is also possible to use their aldimine's as starting materials, that is to say, the products obtained by condensation with primary amines, especially aminobenzenes, in other words, the so-called Schiff bases of the formula in which R is advantageously a benzene radical, for example a phenyl or sulfophenyl radical. Compounds of the formula (5) can be obtained by condensation of the product obtained when formaldehyde and hydrochloric acid are reacted with an amine of the formula with nitrobenzene or a derivative thereof, for example. a nitrobenzene sulfonic acid, in the presence of iron and hydrochloric acid in accordance with Example 17 of U.S. Pat. No. 2,583,551, granted Jan. 29, 1952 to Joseph B. Dickey et al..

in method (b) of the process of the invention the starting materials advantageously used are compounds of the formula CH OH OH awn-Q41 x cn ca oa ocyclic monocarboxylic acid and 1 mol of a halide or an anhydride of an aliphatic, araliphatic or cycloaliphatic monocarboxylic acid, for example, acetyl chloride, acetic anhydride, propionic acid chloride or anhy' dride, chloracetyl chloride, phenoxyacetyl chloride, phenylacetyl chloride or hexahydrobenzoyl chloride or with chloroformic acid phenyl ester. It is also possible, by the use of mixtures of acid halides or acid anhydrides, to produce mixed acylated compounds. Acylation is advantageously carried out in an inert organic solvent, for example, pyridine, benzene, dioxane, isopropyl ether, ethyl acetate or dimethyl formamide. When preparing uniformly acylated compounds, it is also possible to use a large excess of the acylating agent instead of a solvent.

The new dyestuffs are eminently suitable for dyeing and printing fibrous polyester material, especially polyethylene terephthalate, particularly after they have been converted into a state of fine division e.g., by grinding, pasting or reprecipitation. They yield pure, strong, greenish yellow dyeings possessing an excellent fastness to light and to sublimation on such material when applied by the customary dyeing processes, for example, when applied from a dye liquor containing a fine dispersion of the dyestuff and advantageously a dispersing agent at a temperature close to 100C, if desired or required, in the presence of a swelling agent (carrier process), or at a temperature above 100 (up to about 130C) under superatmospheric pressure (hightemperature process). The high degree of light fastness displayed by these dyestuffs is not impaired when they are used in the production of compound shades. for example, green compound shades.

Another attribute of the new dyestuffs is that they produce only a slight tint on wool or any other kind of fiber that may be present in the dyebath, and are thus very suitable for dyeing polyesterwool and polyestercellulose triacetate blends.

The dyestuffs of the invention are also suitable for application by the so-called Thermosol process in which the fabric to be dyed is impregnated preferably at a temperature not exceeding 60C with an aqueous dispersion of the dyestuff, advantageously containing 1 to 50 percent of urea and a thickening agent, especially sodium alginate, and then squeezed in the usual manner, so that the impregnated material advantageously retains 50 to 100 percent of its dry weight of dye liquor. in order to bring about fixation of the dyestuff, the impregnated material is heated to a temperature above 100C, for example, between 180 to 210C, for example, in a current of hot air, it being advantageous to dry the material prior to the heat treatment.

The above-mentioned Thermosol process is specially suitable for the dyeing of union fabrics made of polyester fibers and cellulosic fibers, especially cotton. When dyeing materials of this nature the padding liquor contains dyestuffs suitable for cotton, for example, vat dyestuffs, in addition to a dyestuff of the invention. When operating with vat dyestuffs the padded fabric has to be treated with an aqueous alkaline solution of one of the reducing agents normally used in vat dyeing after it has been subjected to the heat treatment.

The following Examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

Example 1 A solution of 24.18 parts of N:N-bis-(2 hydroxyethyll-m-toluidine dibenzoate in parts of dimethylformamide was added at 0 to 5C to a mixture of 7 parts ofdimethylformamide and 10.2 parts of phosphorus oxychloride and the whole heated for some time at 40 to 45C. After the reaction the products were discharged on to a mixture of parts of ice and 80 parts of water while stirring well, the pH value being adjusted to 6.5 by the addition of sodium hydroxide solution. After some time the oily aldehyde that precipitated was isolated and dried in vacuo.

8.6 Parts of 4-[N:N-bis-(2-hydroxyethyl)-amino]-2- methylbenzaldehyde dibenzoate, l.6 parts of malonic acid dinitrile and 0.2 part of piperidine were heated to the boil under reflux in 12 parts of methanol. The reaction mixture turned a deep yellow. As soon as the reaction had finished the reaction mixture was cooled to 0 to 5C and the precipitated dyestuff of the formula NC CH CH 000-0 H was isolated by filtration, washed with methanol and dried. lt dissolved in organic solvents to form a yellow solution and dyed polyester fibers greenish yellow tints possessing excellent properties of fastness when applied in the form of an aqueous dispersion.

Example 2 8.6 Parts of 4-[N:N-bis-(2'-hydroxyethyl)-amino]-2- methylbenzaldehyde dibenzoate, 2.8 parts of cyanoacetic acid ethyl ester and 0.2 part of piperidine were heated to the boil under reflux in 12 parts of methyl alcohol. As soon as the reaction had finished the reaction mixture was cooled with ice to 0 to 5C. The precipi tated dyestuff was isolated by filtration, washed with methanol and dried. lt dissolved in organic solvents to give a yellow solution and dyed polyester fibers greenish yellow tints possessing very good properties of fastness when applied in the form of a fine dispersion.

Example 3 271 Parts of 4-[N:N-bis-(2 hydroxyethyl)-amino] 2-methylbenzylidene malononitrile were dissolved in 10 parts of pyridine and 422 parts of benzoyl chloride were added to the solution dropwise, The reaction mixture was heated at 80C for about 30 minutes. When cold, the reaction mixture was discharged on to ice and water. The precipitated dyestuff was filtered and washed with dilute aqueous ammonia and water. It was identical with the dyestuff prepared in the manner described in Example 1.

Example 4 I Part of the dyestuff of the formula NC\ /CH GH 0C0C H (a) N oco-c H NC 3 CIi CH 6 5 was ground in the wet state with 2 parts of a 50 percent aqueous solution of sulfite cellulose waste liquor and the mixture was dried.

The dyestuff preparation thus obtained was mixed with 40 parts of a 10 percent aqueous solution of a product obtained by condensing octadecyl alcohol with 20 mols of ethylene oxide and then 4 parts of a 40 per- The following Table gives examples of dyestuffs of the formula 8 -NC\ 2 z (9) fllh kz m Dyestuffs numbered l, 2, 3 4, 5. l8. l9 and 20 were prepared from malonic acid dinitrile and the appropriate aldehyde by the method described in Example I. The remaining dyestuffs in the Table were prepared by the method described in Example 3.

No Y:L Y2 Z1 Z2 Tint l H H green- CH CH 000%; CH CH coo-Q ish yellow 2 0011 H cH cH oco-@ GHZCHZOCOQ 3 CH 00H oH cH 0co@ cH cH 0co-@ 4 0H H cH oH oo0-@ cH cH oco@-c1 5 CH H cH cH 0co-@01 cH cH oco--c1 6 CH H CH2CH2OC cn cn ocoig 7 CH5 H cH cH c co- :H CHZCHZOCO'Q'CH3 II 8 cm H cn cn oco-Q CH2GH20COQ CH3 CH3 h OH on oco-@c ca CH CH oco- -c cn 9 CH3 H ca ca 5 2 2 CH 5 3 1o 0H H cH cH oco-@ocr1 cH cH 0c0-Q -ocH 11 1 2 E l 6 I .Xamp e I NC\ CH CH OCOCH-CH 5.36 Parts of 4 -(dl-B-benzoylhydroxyethylamino)- -C=CH N 2'-methylbenzal-4-anisidine, 0.8 part of malonic acid dinitrile and 0.] part of piperidine were heated at the NC 2 2 boil under reflux for about 6 hours in'20 parts of absolute alcohol. As soon as the reaction had finished the reaction mixture was cooled and the precipitated dyestuff was isolated by filtration, washed with alcohol and dried. It was identical with the dyestuff prepared in the manner described in Example 1.

l claim:

1. A dyestuff of the formula CH=C wherein A is as defined above, B is benzyl, styryl, phenethyl, phenoxymethyl, phenyl, phenyl substituted by a member selected from the group consisting of chlorine, alkyl of l to 4 carbon atoms, lower alkoxy, hydroxy, carbo-lower-alkoxy; B is benzyl, phenethyl, styryl, phenoxymethyl, phenyl or phenyl substituted by a member selected from the group consisting of chlorine, alkyl of l to 4 carbon atoms, lower alkoxy, hydroxy, carbo-lower-alkoxy; and with the provision that when Z is lower alkyl, B is benzyl, phenethyl, phenoxymethyl or phenyl substituted by lower alkoxy and when Z is A O CO B, B is a member selected from the group as defined above.

2. A water-insoluble styryl dyestuff according to claim 1, wherein B is a phenyl group.

3. A water-insoluble styryl dyestuff according to claim 1, wherein Z is a group of the formula A O CO- H. v

4. A water-insoluble dyestuff according to claim 1 7. The styryl dyestuff according to claim I ofthe formula 3 cH oH oco-@-ocri 8. A water-insoluble styryl dyestuff according to claim 1, wherein Z is lower alkyl or A-O-8-B',

wherein A and B are as defined in claim 1.

9. A water-insoluble styryl dyestuff according to claim 1, wherein B is phenyl, phenyl substituted by a member selected from the group consisting of chlorine, alkyl of l to 4 carbon atoms, methoxy, hydroxy, and carbo-lower-alkoxy.

10. A water-insoluble styryl dyestuff according to claim 1, wherein X is a methyl group.

11. The styryl dyestuff of the formula N CH CH j=CH I NC CH CH-CH QCO CH l 12. A dyestuff of the formula:

wherein A is an ethylene group.

5. A water-insoluble dyestuff according to claim 1 of the formula 6. The styryl dyestuff according to claim 1 of the formula wherein X is hydrogen, methyl or methoxy; A is a lower alkylene of2 to 4 carbon atoms; R, is a lower alkyl and R is a lower alkyl or wherein R and A are as defined above. 

1. A DYESTUFF OF THE FORMULA
 2. A water-insoluble styryl dyestuff according to claim 1, wherein B is a phenyl group.
 3. A water-insoluble styryl dyestuff according to claim 1, wherein Z is a group of the formula A- O- CO- B''.
 4. A water-insoluble dyestuff according to claim 1 wherein A is an ethylene group.
 5. A water-insoluble dyestuff according to claim 1 of the formula
 6. The styryl dyestuff according to claim 1 of the formula
 7. The styryl dyestuff according to claim 1 of the formula
 8. A water-insoluble styryl dyestuff according to claim 1, wherein Z is lower alkyl or
 9. A water-insoluble styryl dyestuff according to claim 1, wherein B is phenyl, phenyl substituted by a member selected from the group consisting of chlorine, alkyl of 1 to 4 carbon atoms, methoxy, hydroxy, and carbo-lower-alkoxy.
 10. A water-insoluble styryl dyestuff according to claim 1, wherein X is a methyl group.
 11. The styryl dyestuff of the formula
 12. A dyestuff of the formula: 